Sugar compositions

ABSTRACT

A sugar composition comprising at least 40% dissolved solids in an aqueous solution having a viscosity at least 10% lower than a 42 DE (Dextrose Equivalents) reference solution with a same dissolved solids concentration at a given temperature. Another sugar composition comprising at least 30% glucose relative to total sugars, at least 10% mannose relative to total sugars, at least 5% xylose relative to total sugars, and less than 0.25% ash. Another sugar composition comprising at least 30% glucose relative to total sugars at least 10% mannose relative to total sugars, at least 5% xylose relative to total sugars, and at least 2% total furfurals.

RELATED APPLICATIONS

In accord with the provisions of 35 U.S.C. §119(e) and §363, thisapplication claims the benefit of:

U.S. 61/545,389 filed Oct. 10, 2011 by Aharon EYAL and entitled “SugarCompositions And Uses Thereof”; which is fully incorporated herein byreference.

This application is related to the following co-pending applications:

Prior PCT application IL 2011/000424 filed on Jun. 1, 2011 by RobertJANSEN et al. and entitled “LIGNIN COMPOSITIONS, SYSTEMS AND METHODS FORPROCESSING LIGNIN AND/OR HCl” and published as WO/2011/151823;

Prior PCT application IL 2011/000509 filed on Jun. 26, 2011 by AharonEYAL et al. and entitled “SUGAR MIXTURES AND METHODS FOR PRODUCTION ANDUSE THEREOF” and published as WO 2011/161685;

Prior PCT application IL 2011/000517 filed on Jun. 28, 2011 by AharonEYAL et al. and entitled “METHODS AND SYSTEMS FOR PROCESSING A SUCROSECROP AND SUGAR MIXTURES” and published as WO2012/001688;

Prior PCT application US 2011/046153 filed on Aug. 1, 2011 by RobertJANSEN et al. and entitled “METHODS AND SYSTEMS FOR SOLVENTPURIFICATION” and published as WO 2012/018740;

Prior US application U.S. Ser. No. 13/195,721 filed on Aug. 1, 2011 byRobert JANSEN et al. and entitled “METHODS AND SYSTEMS FOR SOLVENTPURIFICATION” and published as US 2012/0167874;

Prior PCT application US2011/057552 filed on May 9, 2011 by RobertJANSEN et al. and entitled “HYDROLYSIS SYSTEMS AND METHODS” andpublished as WO2012/061085;

Prior PCT application PCT/US2011/064237 filed on Dec. 9, 2011 by AharonEYAL et al. and entitled “METHODS AND SYSTEMS FOR PROCESSINGLIGNOCELLULOSIC MATERIALS” and published as WO2012/079021;

Prior PCT application US2012/024033 filed on Feb. 6, 2012 by RobertJANSEN et al. and entitled “SYSTEMS AND METHODS FOR SUGAR REFINING”; andpublished as WO/2012/106727; each of which is fully incorporated hereinby reference.

FIELD OF THE INVENTION

This invention relates to sugar compositions.

BACKGROUND OF THE INVENTION

The increasing cost of fossil fuels has created a demand for alternativeenergy sources. This demand is reflected in the Renewable Fuel Standard(RFS), established by the U.S. Environmental Protection Agency (EPA)under the Energy Independence and Security Act of 2007. RFS has setstandards to increase the volume of renewable fuel required to beblended into gasoline from 9 billion gallons in 2008 to 36 billiongallons by 2022, composed of 15 billion gallons of renewable fuel and 21billion gallons of advanced bio-fuels (16 billion gallons cellulosicbio-fuels).

One theoretically feasible way to produce alternative fuels is bychemical conversion of carbon containing substrates using non-enzymaticcatalysts. In practice, development of this technology has revealed avariety of technical problems including, but not limited to, fouling orpoisoning of catalysts, unacceptably low yields of conversion productand requirements for reaction conditions which make the conversionprocess industrially unattractive.

SUMMARY OF THE INVENTION

A broad aspect of the invention relates to sugar compositions. In someexemplary embodiments of the invention, the compositions are useful assubstrates for chemically catalyzed conversion processes. In someembodiments, the sugars in the compositions result from hydrolysis of acellulose containing substrate (e.g. with HCl).

As used in this specification and the accompanying claims the term“hydrolyzate” refers to a mixture of sugars resulting from hydrolysis ofa cellulose containing substrate. The term hydrolyzate includes “refinedhydrolyzates” prepared by application of an appropriate purificationprotocol to remove residual reagents from the hydrolysis process and/orseparate lignin (if present) and/or adjust the sugar concentration to adesired level and/or adjust the sugar composition by enzymaticconversion. Exemplary purification protocols are described in co-pendingInternational application publication WO/2012/106727 which is fullyincorporated herein by reference. Alternatively or additionally, theterm hydrolyzate includes fractionated hydrolyzates which are enrichedfor one or more specific sugars (e.g. glucose or mannose) or sugar types(e.g. pentoses or hexoses). In some exemplary embodiments of theinvention, hydrolyzates are provided as aqueous solutions. According tovarious exemplary embodiments of the invention, the concentration ofsugars in such an aqueous solution is 40%, 50%, 60%, 70% or 80% orintermediate or greater percentages. For example, in some embodimentsthe sugar concentration is 40 to 50%, 50 to 60%, 60 to 70%, 70 to 80% orgreater than 80% In other exemplary embodiments of the invention,hydrolyzates are provided as a dry sugar mixture. Dried sugar mixturescan be prepared, for example, by spray drying and/or crystallization. Insome embodiments, a dried sugar mixture is subsequently dissolved inwater, or an aqueous solution, at a desired concentration.

As used in this specification and the accompanying claims the term“cellulose containing substrate” includes any plant derived materialcontaining cellulose (e.g. wood, wood by-products, crop residues (e.g.cornstover, sugar cane bagasse, empty palm fruit bunches), perennialgrasses, perennial woody crops and food/feed processing residues) aswell as processed cellulose products (e.g. paper and cardboard)).

As used in this specification and the accompanying claims the term“cellulose sugars” refers to glucose in monomeric form and that portionof any dimer or higher oligomer composed of glucose.

As used in this specification and the accompanying claims the term“hemicellulose sugars” refers to xylose and/or arabinose and/or mannosein monomeric form and that portion of any dimer or higher oligomercomposed of xylose and/or arabinose and/or mannose.

One aspect of some embodiments of the invention relates to sugarmixtures characterized by a low viscosity relative to previouslyavailable alternatives with a same dissolved solids concentration and 42DE (Dextrose Equivalents) when assayed at the same temperature.

Another aspect of some embodiments of the invention relates to a sugarmixture containing a low level of inorganic material. In some exemplaryembodiments of the invention, a reduction in the level of inorganicmaterial in a sugar mixture contributes to a decrease in catalystfouling and/or poisoning during the conversion process. In someexemplary embodiments of the invention, levels of sulfur are below 50PPM, 40 PPM, 30 PPM, 20 PPM or 10 PPM (e.g. 10 to 50 PPM; 20 to 40 PPM;35 to 50 PPM or 40 to 50 PPM). Alternatively or additionally, in someexemplary embodiments of the invention, levels of phosphorus are below10 PPM, 7 PPM, 5 PPM or 1 PPM (e.g. 1 to 10 PPM; 1 to 7 PPM or 1 to 5PPM or 5 to 10 PPM).

Another aspect of some embodiments of the invention relates to a levelof furfurals present in the sugar mixture. As used in this specificationand the accompanying claims the terms “furfurals” and “total furfurals”include both furfural and hydroxymethylfurfural. In those cases where“furfural” or “hydroxymethylfurfural” amounts or concentrations areindicated, reference is to the specific compound. In some exemplaryembodiments of the invention, furfural is present due to hydrolysis ofpentose-comprising polysaccharides. According to various exemplaryembodiments of the invention 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 percent (orintermediate percentages) of pentoses (e.g. from hemicellulose) aredegraded during the hydrolysis reaction and the resultant furfuralappears in the hydrolyzate. Alternatively or additionally, in someexemplary embodiments of the invention, hydroxymethylfurfural is presentdue to hydrolysis of hexose-comprising polysaccharides (e.g. celluloseand/or hemicellulose). According to various exemplary embodiments of theinvention According to various exemplary embodiments of the invention 1,2, 3, 4, 5, 6, 7, 8, 9 or 10 (or intermediate percentages) of hexosesare degraded during the hydrolysis reaction and the resultanthydroxymethylfurfural appears in the hydrolyzate.

One aspect of some embodiments of the invention relates to hydrolyzateswith a saccharide composition that is different than the theoreticallyexpected saccharide yield from hydrolysis of the cellulose containingsubstrate. For example, if the substrate is wood, the hydrolyzate mayhave less glucose that expected and/or more pentoses than expected. Insome exemplary embodiments of the invention, the hydrolyzate resultsfrom complete hydrolysis of hemicellulose but incomplete hydrolysis ofcellulose. In some embodiments, hemicellulose and cellulose arehydrolyzed separately and the resultant hemicellulose hydrolyzate andcellulose hydrolyzate are mixed in a desired ratio to produce ahydrolyzate according to an exemplary embodiment of the invention. Insome embodiments, the hydrolyzate composition is affected by sugarsdegradation rate during the hydrolysis. Some of the sugars in thecellulose containing substrate (e.g. lignocellulose) substrate degradeat a higher rate compared with other sugars. In some embodiments,pentoses degrade more rapidly than hexoses.

An additional aspect of some embodiments of the invention relates tosucrose present with the cellulose containing substrate prior tohydrolysis. In some exemplary embodiments of the invention, this resultsfrom incomplete processing of a sucrose crop as described in co-pendingapplication publication WO2012/001688; which is fully incorporatedherein by reference. In some exemplary embodiments of the invention,this sucrose contributes to an increase in fructose in the hydrolyzate.Alternatively or additionally, in some embodiments an enzymatictreatment is employed to increase sucrose levels. Exemplary enzymatictreatments are described hereinbelow.

Another aspect of some embodiments of the invention relates to assayingone or more specific parameters of a hydrolyzate produced in anindustrial facility and using results of the assay to select a subset ofhydrolyzate batches for chemical conversion. In some embodiments,batches which are not well suited to biological conversion (e.g.fermentation) are advantageously employed in chemical conversion.According to various exemplary embodiments of the invention, the one ormore specific parameters assayed include viscosity and/or ash contentand/or level(s) of one or more degradation product(s) and/or levels ofone or more hemicellulose sugars. Degradation products include, but arenot limited to, furfural and hydroxymethylfurfural.

It will be appreciated that the various aspects described above relateto solution of technical problems associated with conversion ofcarbohydrates in a chemically catalyzed reaction.

Alternatively or additionally, it will be appreciated that the variousaspects described above relate to solution of technical problems relatedto fouling and/or poisoning of catalysts in a chemically catalyzedreaction.

In some exemplary embodiments of the invention, there is provided asugar composition including: at least 40%, at least 50%, at least 60% orat least 70% dissolved solids in an aqueous solution having a viscosityat least 10% lower than a 42 DE (Dextrose Equivalents) referencesolution with a same dissolved solids concentration at a giventemperature (e.g. a 42% high fructose 80% solids corn syrup referencesolution has a viscosity of 2200 cP at 80° F.).

In some embodiments, the dissolved solids include at least 20%, at least30%, at least 40% or at least 50% hemicellulose sugars. Alternatively oradditionally, in some embodiments, mannose comprises at least 10%, atleast 15%, at least 20%, at least 25% or at least 30% of the dissolvedsolids and/or xylose comprises at least 5%, at least 7.5%, at least 10%,at least 12.5% or at least 15% of the dissolved solids. Alternatively oradditionally, in some embodiments glucose comprises not more than 60% ornot more than 55% of the dissolved solids. Alternatively oradditionally, in some embodiments at least 90% of the dissolved solidsare monomeric sugars. Alternatively or additionally, in some embodimentsthe composition includes at least 5, at least 10 or at least 15% oforganic compounds including one or more compounds selected from thegroup consisting of alcohols, ketones, aldehydes and organic acidsincluding 2-5 carbon atoms.

In some exemplary embodiments of the invention, there is provided asugar composition including: at least 30%, at least 40%, at least 50% orat least 60% glucose relative to total sugars; at least 10%, at least15%, at least 20%, at least 25% or at least 30% mannose relative tototal sugars; at least 5%, at least 7.5%, at least 10%, at least 12.5%or at least 15% xylose relative to total sugars; and less than 0.25,less than 0.20, less than 0.15, less than 0.10, less than 0.05, lessthan 0.01 or less than 0.005% ash. In some embodiments, the compositionincludes less than 50, less than 30, less than 10, less than 5 or lessthan 1 PPM sulfur. Alternatively or additionally, in some embodimentsthe composition includes less than 10, less than 5, less than 3 lessthan 1 or less than 0.1 PPM phosphorus. Alternatively or additionally,in some embodiments the composition is provided as a solution includingat least 40%, at least 50%, at least 60% or at least 70% dissolvedsolids. Alternatively or additionally, in some embodiments thecomposition includes at least 5, at least 10 or at least 15% of organiccompounds including one or more compounds selected from the groupconsisting of alcohols, ketones, aldehydes and organic acids including2-5 carbon atoms.

In some exemplary embodiments of the invention, there is provided asugar composition including: at least 30%, at least 40%, at least 50% orat least 60% glucose relative to total sugars; at least 10%, at least15%, at least 20%, at least 25% or at least 30% mannose relative tototal sugars; at least 5%, at least 7.5%, at least 10%, at least 12.5%or at least 15% xylose relative to total sugars; and at least 2%, atleast 3%, at least 4% or at least 5% total furfurals. In someembodiments, the composition includes not more than 15, not more than12, or not more than 10% total furfurals. Alternatively or additionally,in some embodiments a molar ratio of furfural to pentoses is at least0.03, at least 0.05, at least 0.07 or at least 0.09. Alternatively oradditionally, in some embodiments a molar ratio of furfural to pentosesis less than 0.12 or less than 0.1. Alternatively or additionally, insome embodiments a molar ratio of hydroxymethylfurfural to hexoses is atleast 0.03, at least 0.05, at least 0.07 or at least 0.09. Alternativelyor additionally, in some embodiments a molar ratio ofhydroxymethylfurfural to hexoses is less than 0.12 or less than 0.1.Alternatively or additionally, in some embodiments a molar ratio ofcarboxylic acids (e.g. acetic and/or formic and/or galactauronic and/orlevulinic acids) to sugars is at least 0.03, at least 0.05, at least0.07 or at least 0.09. Alternatively or additionally, in someembodiments a molar ratio of carboxylic acids to sugars is less than0.12 or less than 0.1.

In some exemplary embodiments of the invention, there is provided asugar composition, including: at least 30, at least 40, at least 50 , atleast 60 or at least 70% hemicellulose sugars relative to total sugars;and 20 to 60% cellulose sugars relative to total sugars. In someembodiments, the composition includes at least 10%, at least 15%, atleast 20%, at least 25% or at least 30% mannose relative to totalsugars. Alternatively or additionally, in some embodiments thecomposition includes at least 5%, at least 7.5%, at least 10%, at least12.5% or at least 15% xylose relative to total sugars. Alternatively oradditionally, in some embodiments the composition includes at least 5%,at least 7.5%, at least 10%, at least 12.5% or at least 15% fructoserelative to total sugars.

In some exemplary embodiments of the invention, there is provided asugar composition including at least 10% fructose relative to totalsugars; and at least 10% hemicellulose sugars relative to total sugars.In some embodiments, the composition includes at least 15% or at least20% fructose. Alternatively or additionally, in some embodiments thecomposition includes at least 15% or at least 20% hemicellulose sugars.Alternatively or additionally, in some embodiments the composition isprovided as an aqueous solution including at least 60% dissolved solids.Alternatively or additionally, in some embodiments the compositionincludes at least 5, at least 10 or at least 15% of organic compoundsincluding one or more compounds selected from the group consisting ofalcohols, ketones, aldehydes and organic acids including 2-5 carbonatoms.

In some exemplary embodiments of the invention, there is provided asugar composition comprising (relative to dry solids): (a) at least 49%glucose; (b) at least 9.5% xylose; (c) at least 2.5% arabinose; and (d)at least 25% mannose.

In some exemplary embodiments of the invention, there is provided amethod including: producing a sugar composition as describedhereinabove; and converting sugars in the sugar composition to aconversion product in a chemically catalyzed reaction. In someembodiments, the producing includes hydrolyzing a substrate includingcellulose to produce a hydrolyzate. In some embodiments, the hydrolyzingincludes refining the hydrolyzate.

In some exemplary embodiments of the invention, there is provided amethod including

hydrolyzing not more than 90% of cellulose in a cellulose includingsubstrate to produce a hydrolyzate; and

converting sugars in the hydrolyzate to a conversion product in achemically catalyzed reaction.

In some exemplary embodiments of the invention, there is provided amethod including: providing a conversion product as describedhereinabove; and processing the conversion product to produce aprocessed product.

According to various exemplary embodiments of the invention, theprocessed product includes one or more members selected from the groupconsisting of terephthalic acid, polymers of terephthalic acid, a fuelingredient, a paraffin a polyethylene, a polystyrene, a polypropylene,butyl acrylate, butyl acetate, dibutyl phthalate, dibutyl sebacate,other butyl esters, ethylene glycol, monobutyl ether, di-ethyleneglycol, triethylene glycol, monobutyl ether, isobutyl acetate andbutanone (MEK).

In some exemplary embodiments of the invention, there is provided aprocessed product produced by a method as described hereinabove.

In some exemplary embodiments of the invention, there is provided amethod including

providing a processed product as described hereinabove; and

subjecting the processed product to an industrial process to produce adownstream product.

According to various exemplary embodiments of the invention, thedownstream product is selected from the group consisting of a liquidfuel and a polymeric plastic.

In some exemplary embodiments of the invention, there is provided adownstream product produced by a method as described hereinabove.

In some exemplary embodiments of the invention, there is provided amethod including

providing a processed product as described hereinabove; and

using the processed product as an ingredient or component in adownstream product. According to various exemplary embodiments of theinvention, the downstream product is selected from the group consistingof a liquid fuel, a super absorbent gel, a paint, a dye, a glue, afabric and a plastic item.

In some exemplary embodiments of the invention, there is provided adownstream product produced by a method as described hereinabove.

REPRESENTATIVE EMBODIMENTS

The following embodiments of the disclosure are provided by way ofexample only:

1. A sugar composition comprising:

at least 40% dissolved solids in an aqueous solution having a viscosityat least 10% lower than a 42 DE (Dextrose Equivalents) referencesolution with a same dissolved solids concentration at a giventemperature.

2. A composition according to embodiment 1, wherein the dissolved solidscomprise at least 20% hemicellulose sugars.

3. A composition according to embodiment 1 or embodiment 2, whereinmannose comprises at least 10% of the dissolved solids and/or xylosecomprises at least 5% of the dissolved solids.

4. A composition according to any of embodiments 1 to 3, wherein glucosecomprises less than 60% of the dissolved solids.

5. A composition according to any of embodiments 1 to 4, wherein atleast 90% of the dissolved solids are monomeric sugars.

6. A composition according to any of embodiments 1 to 5, comprising atleast 5% of organic compounds comprising one or more compounds selectedfrom the group consisting of alcohols, ketones, aldehydes and organicacids comprising 2-5 carbon atoms.

7. A sugar composition comprising:

at least 30% glucose relative to total sugars;

at least 10% mannose relative to total sugars;

at least 5% xylose relative to total sugars; and

less than 0.25% ash.

8. A composition according to embodiment 7, comprising less than 50 PPMsulfur.

9. A composition according to embodiment 7 or 8, comprising less than 10PPM phosphorus.

10. A composition according to any of embodiments 7 to 9, provided as asolution comprising at least 40% dissolved solids.

11. A composition according to any of embodiments 7 to 10, furthercomprising at least 5% of organic compounds comprising one or morecompounds selected from the group consisting of alcohols, ketones,aldehydes and organic acids comprising 2-5 carbon atoms.

12. A sugar composition comprising:

at least 30% glucose relative to total sugars;

at least 10% mannose relative to total sugars;

at least 5% xylose relative to total sugars; and

at least 2% total furfurals.

13. A composition according to embodiment 12, comprising not more than15% total furfurals.

14. A composition according to embodiment 12 or 13, wherein a molarratio of furfural to pentoses is at least 0.03.

15. A composition according to any of embodiments 12 to 14, wherein amolar ratio of furfural to pentoses is less than 0.12.

16. A composition according to any of embodiments 12 to 15, wherein amolar ratio of hydroxymethylfurfural to hexoses is at least 0.03.

17. A composition according to any of embodiments 12 to 16, wherein amolar ratio of hydroxymethylfurfural to hexoses is less than 0.12.

18. A composition according to any of embodiments 12 to 17, wherein amolar ratio of carboxylic acids to sugars is at least 0.03.

19. A composition according to any of embodiments 12 to 18, wherein amolar ratio of carboxylic acids to sugars is less than 0.12.

20. A sugar composition, comprising:

at least 30% hemicellulose sugars relative to total sugars; and

20% to 60% cellulose sugars relative to total sugars.

21. A composition according to embodiment 20, comprising at least 10%mannose relative to total sugars.

22. A composition according to embodiment 20 or 21, comprising at least5% xylose relative to total sugars.

23. A composition according to any of embodiments 20 to 22, comprisingat least 5% fructose relative to total sugars.

24. A sugar composition comprising:

at least 10% fructose; and

at least 10% hemicellulose sugars.

25. A composition according to embodiment 24, comprising at least 15%fructose.

26. A composition according to embodiment 24 or 25, comprising at least15%, hemicellulose sugars.

27. A composition according to any of embodiments 24 to 26, provided asan aqueous solution comprising at least 60% dissolved solids.

28. A composition according to any of embodiments 24 to 27, furthercomprising at least 5% of organic compounds comprising one or morecompounds selected from the group consisting of alcohols, ketones,aldehydes and organic acids comprising 2-5 carbon atoms.

29. A sugar composition comprising (relative to dry solids):

(a) at least 49% glucose;

(b) at least 9.5% xylose;

(c) at least 2.5% arabinose; and

(d) at least 25% mannose.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although suitable methods andmaterials are described below, methods and materials similar orequivalent to those described herein can be used in the practice of thepresent invention. In case of conflict, the patent specification,including definitions, will control. All materials, methods, andexamples are illustrative only and are not intended to be limiting.

As used herein, the terms “comprising” and “including” or grammaticalvariants thereof are to be taken as specifying inclusion of the statedfeatures, integers, actions or components without precluding theaddition of one or more additional features, integers, actions,components or groups thereof.

The phrase “adapted to” as used in this specification and theaccompanying claims imposes additional structural limitations on apreviously recited component.

Percentages (%) of insoluble carbohydrates (e.g. cellulose), sugars,saccharides, furfurals and ash (total and individual components) are W/W(weight per weight) relative to total solids unless otherwise indicated.Concentrations indicated in PPM are also on a total solids basis unlessotherwise indicated. As used in this specification and the accompanyingclaims the term “total solids” indicates dry matter which remains afterall water is evaporated.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to understand the invention and to see how it may be carriedout in practice, embodiments will now be described, by way ofnon-limiting example only, with reference to the accompanying figures.In the figures, identical and similar structures, elements or partsthereof that appear in more than one figure are generally labeled withthe same or similar references in the figures in which they appear.Dimensions of components and features shown in the figures are chosenprimarily for convenience and clarity of presentation and are notnecessarily to scale. The attached figures are:

FIG. 1 is schematic overview of a system according some exemplaryembodiments of the invention; and

FIG. 2 is a simplified flow diagram of a method according to someexemplary embodiments of the invention.

DETAILED DESCRIPTION OF EMBODIMENTS

Embodiments of the invention relate to sugar compositions. According tovarious exemplary embodiments of the invention the sugar compositionsare provided in liquid or solid form.

Specifically, sugar compositions according to various embodiments of theinvention can serve as input streams for chemical conversion to aconversion product. Some exemplary embodiments of the invention relateto conversion products produced by such a chemical conversion. Exemplaryconversion products include, but are not limited to hydrocarbons (e.g.para-xylene), oxygenated hydrocarbons, non-condensable gas products,alcohols and hydrogen gas. In some exemplary embodiments of theinvention, these conversion products are characterized by an O/C ratioless than 1.5; less than 1.0; less than 0.75; less than 0.5; less than0.3; less than 0.2 or less than 0.1.

Compositions according to exemplary embodiments of the invention may bebetter understood with reference to the drawings and accompanyingdescriptions.

Before explaining at least one embodiment of the invention in detail, itis to be understood that the invention is not limited in its applicationto the details set forth in the following description or exemplified bythe Examples. The invention is capable of other embodiments or of beingpracticed or carried out in various ways. Also, it is to be understoodthat the phraseology and terminology employed herein is illustrative andnot limiting.

Exemplary System Overview

FIG. 1 is a simplified schematic diagram of a system for acid hydrolysisof a substrate including cellulose indicated generally as 100. Depictedsystem 100 includes a main hydrolysis reactor 110 adapted to receive aninput substrate 112. In many cases substrate 112 is provided as woodchips, although any cellulose containing substrate can be used insteadof wood. In some exemplary embodiments of the invention, substrate 112is subjected to a pretreatment in pretreatment module 108 to produce amodified substrate 112′. In some embodiments, a pretreatment conductedin module 108 produces one or more streams containing ash and/or sugars(additional streams not depicted). Exemplary pretreatments are describedin international application publication WO/2012/079021; which is fullyincorporated herein by reference.

Additional exemplary substrates 112 include, but are not limited to,sugar cane bagasse, sugar beets and/or their cossettes, corn stover,post harvest plants (e.g. cotton, soybean or rapeseed), switchgrass,broomgrass, paper and cardboard.

In the depicted exemplary system, substrate 112 is brought into contactwith a concentrated HCl solution in reactor 110 and hemicellulose and/orcellulose in the substrate are hydrolyzed to produce a mixture ofsoluble sugars and, optionally, residual lignin. These materials arecollected separately as lignin stream 120 (if present) and crudehydrolyzate 130, each of which contains a high concentrations of HCl.

Details of exemplary hydrolysis methods and systems are described inco-pending International application publication WO2012/061085; which isfully incorporated herein by reference. According to various exemplaryembodiments of the invention the way in which hydrolysis is conducted inreactor 110 contributes to the composition of crude hydrolyzate 130and/or lignin stream 120. Affecting parameters include, but are notlimited to, initial substrate moisture, reactor design, mode ofhydrolysis (e.g. co-current contact, counter-current contact andcombinations thereof), number of hydrolysis stages and acidconcentration and/or temperature and/or residence time in eachhydrolysis stage. The composition of crude hydrolyzate 130 and/or ligninstream 120 is influenced by the amount of sugar degradation productsproduced at 110 and/or 201 and/or by the yield of specific intact sugarsproduced at 110 and/or remaining after 201 (e.g. pentoses such as xyloseand/or hexoses such as glucose).

Crude hydrolyzate 130 is processed to remove HCl and/or adjust themixture to achieve one or more desired ratios of mixture components(e.g. disaccharides and/or monosaccharides). Parameters of HCl removalalso affect the composition of the deacidified hydrolyzate, includingthe mode of removal, e.g. distillation vs. solvent extraction, solventchoice, e.g. its selectivity and water co-extraction, contactors design,number of theoretical stages in the solvent extraction, temperature ofeach stage and residence time in each stage. This processing isconducted in a hydrolyzate refining module, designated here genericallyas 201.

In some embodiments, additional hydrolyzate (similar to 130) isrecovered from lignin stream 120 as described in co-pendingInternational application publication WO/2011/151823 which is fullyincorporated herein by reference. In some exemplary embodiments of theinvention, this additional hydrolyzate is routed (not depicted) torefining module 201. According to various exemplary embodiments of theinvention this additional hydrolyzate increases a total sugar yieldand/or changes a composition of mixture (e.g. refined hydrolyzate 230).

In depicted system 100, hydrolyzate refining module 201 employs a flowof organic solvent 155 (solid arrows) to extract HCl 140 (dashed arrows)from crude hydrolyzate 130.

Refined hydrolyzate 230 containing a mixture of de-acidified sugars isthe primary product of refining module 201. In some embodiments, sugarsrecovered from pretreatment module 108 and/or lignin stream 120 are alsopresent in refined hydrolyzate 230. Module 201 also produces a stream ofHCl 140 mixed with solvent 155 (depicted as parallel dashed and solidarrows respectively for clarity) which is routed to a solvent/HClrecovery module 150. Recovery module 150 separates HCl 140 from solvent155. In some exemplary embodiments of the invention, separation is bydistillation. HCl 140 is recycled to hydrolysis reactor 110 and solvent155 is recycled to refining module 201. Details of HCl and solventrecycling are described in co-pending international applicationpublication WO/2012/081740 and US application publication 2012/0167874;each of which is fully incorporated by reference.

Refined hydrolyzate 230 includes a mixture of de-acidified sugars.Various components of the mixture can be chemically converted toconversion products. In some cases, implementation of specific chemicalconversion processes is influenced by an initial composition of refinedhydrolyzate 230. In many cases, refined hydrolyzate 230 contains glucoseas a primary component since glucose is a primary component of cellulosein substrate 112. Alternatively or additionally, in many cases, sugarmixture 230 contains a significant amount of xylose since xylose isoften the most prevalent saccharide component of hemicellulose insubstrate 112.

In some exemplary embodiments of the invention, refined hydrolyzate 230is assayed with respect to one or more parameters in an assay module211. Depending upon the results of the assay(s), refined hydrolyzate 230is routed to chemical conversion 233 or biological conversion 235 (e.g.fermentation).

Exemplary Chemical Conversion Processes

Exemplary chemically catalyzed processes for conversion of biomassderived sugars to conventional liquid fuels through a multistepcatalytic conversion process are disclosed in U.S. Pat. No. 7,038,094;U.S. Pat. No. 6,486,366; U.S. Pat. No. 6,479,713; U.S. Pat. No.8,277,643; U.S. Pat. No. 7,880,049; U.S. Pat. No. 4,503,278; U.S. Pat.No. 8,017,818; U.S. Pat. No. 7,977,517; U.S. Pat. No. 7,038,094; U.S.Pat. No. 6,841,085; U.S. Pat. No. 6,124,443; U.S. Pat. No. 8,084,508;U.S. Pat. No. 6,136,868; U.S. Pat. No. 5,856,261; U.S. Pat. No.8,277,643; U.S. Pat. No. 7,947,858; U.S. Pat. No. 7,704,381; U.S. Pat.No. 5,856,261; U.S. Pat. No. 8,152,867; U.S. Pat. No. 7,935,156; U.S.Pat. No. 7,942,940; U.S. Pat. No. 8,026,378; U.S. Pat. No. 8,053,468;U.S. Pat. No. 8,084,635; U.S. Pat. No. 8,178,701; and U.S. Pat. No.8,188,030. The contents of each of these patents are fully incorporatedherein by reference.

Exemplary Compositions

Some exemplary embodiments of the invention, relate to sugarcompositions suitable for use as inputs in a catalytic conversionprocesses.

In some exemplary embodiments of the invention, the sugar compositionincludes at least 40%, at least 50%, at least 60% or at least 70%dissolved solids in an aqueous solution having a viscosity which is atleast 10%, 20%, 30%, 40% or 50% lower than a 42 DE (DextroseEquivalents) solution with a same dissolved solids concentration at agiven temperature. Viscosity influences flow properties which may berelevant to conversion processes 233 and/or 235. According to variousexemplary embodiments of the invention the dissolved solids comprise atleast 20%, at least 30%, at least 40% or at least 50% hemicellulosesugars.

In some exemplary embodiments of the invention, at least 10%, 15%, 20%,25% or 30% (or intermediate or greater percentages) of the dissolvedsolids are mannose. Alternatively or additionally, at least 5%, 7.5%,10%, 12.5% or 15% (or intermediate or greater percentages) of thedissolved solids are xylose. According to various exemplary embodimentsof the invention mannose and xylose are present as monomeric sugarsand/or as portions of oligomeric sugars (dimers or higher).

In some exemplary embodiments of the invention, less than 60%, or lessthan 55%, of the dissolved solids is glucose.

Alternatively or additionally, the dissolved solids in the compositioninclude at least 90%, at least 92% or at least 94% monomeric sugars.

Alternatively or additionally, in some embodiments the compositionincludes at least 5%, 6%, 7%, 8%, 9% or 10% of organic compounds such asalcohols and/or ketones and/or aldehydes and/or organic acids comprising2-5 carbon atoms.

Some exemplary embodiments of the invention relate to a compositionincluding at least 30%, 40%, 50% or 60% (or intermediate or greaterpercentages) glucose relative to total sugars, at least 10%, at least15%, at least 20%, at least 25%, at least 30% (or intermediate orgreater percentages) mannose relative to total sugars and at least 5%,at least 7.5%, at least 10%, at least 12.5% or at least 15% (orintermediate or greater percentages) xylose relative to total sugars andless than 0.25% or less than 0.15% ash. In some embodiments,compositions of this type include less than 50, less than 10, less than5 or less than 2 PPM sulfur (or intermediate or lower amounts).Alternatively or additionally, compositions of this type include lessthan 10, less than 7, less than 5, less than 2 or less than 1PPMphosphorus (or intermediate or lower amounts). Alternatively oradditionally, in some embodiments compositions of this type are providedas an aqueous solution with at least 40%, at least 50%, at least 60%, atleast 70% dissolved solids (or intermediate or higher percentages).

Alternatively or additionally, in some embodiments the compositionincludes at least 5%, 6%, 7%, 8%, 9% or 10% of organic compounds such asalcohols and/or ketones and/or aldehydes and/or organic acids comprising2-5 carbon atoms.

Some exemplary embodiments of the invention relate to a sugarcomposition including at least 30%, at least 40%, at least 50% or atleast 60% glucose (or intermediate or higher percentages) relative tototal sugars and at least 2%, at least 3%, at least 4%, at least 5%total furfurals (or intermediate or higher percentages).

In some exemplary embodiments of the invention, the composition includesat least 10%, at least 15%, at least 20%, at least 25% or at least 30%mannose (or intermediate or higher percentages) relative to totalsugars. Alternatively or additionally, in some exemplary embodiments ofthe invention the composition includes at least 5%, at least 7.5%, atleast 10%, at least 12.5% or at least 15% xylose (or intermediate orhigher percentages) relative to total sugars.

In some embodiments, the composition includes not more than 15 or notmore than 10% total furfurals. In some exemplary embodiments of theinvention, a molar ratio of furfural to pentoses is at least 0.03, 0.05,0.06, 0.065, 0.07 or at least 0.075. Alternatively or additionally, themolar ratio of furfural to pentoses is less than 0.12, 0.115, 0.11,0.105 or less than 0.1. Alternatively or additionally, a molar ratio ofhydroxymethylfurfural to hexoses is at least 0.03, 0.05, 0.06, 0.065,0.07 or at least 0.075. Alternatively or additionally, a molar ratio ofhydroxymethylfurfural to hexoses is less than 0.12 or less than 0.1. Insome embodiments, compositions of this type are provided as an aqueoussolution with at least 40%, at least 50%, at least 60% or at least 70%dissolved solids (or intermediate or higher percentages).

In some embodiments, a molar ratio of carboxylic acids to sugars in thecomposition is at least 0.03. Alternatively or additionally, in someembodiments a molar ratio of carboxylic acids to sugars in thecomposition is less than 0.12.

Some exemplary embodiments of the invention relate to a sugarcomposition including at least 30%, at least 40%, at least 45% or atleast 50% (or intermediate or higher percentages) hemicellulose sugars(relative to total sugars) and 20%, 30%, 40%, 50%, 55% or 60% (orintermediate or higher percentages) glucose (relative to total sugars).Alternatively or additionally, in some embodiments a composition of thistype includes at least 10%, at least 15%, at least 20%, at least 25% orat least 30% (or intermediate or higher percentages) mannose (relativeto total sugars) and/or at least 5%, at least 7.5%, at least 10%, atleast 12.5% or at least 15% (or intermediate or higher percentages)xylose (relative to total sugars). Alternatively or additionally, acomposition of this type includes 5%, at least 7.5%, at least 10%, atleast 12.5% or at least 15% (or intermediate or higher percentages)fructose (relative to total sugars). In some embodiments, fructoseresults from use of a hydrolysis substrate 112 (FIG. 1) includingsucrose as described in International application publicationWO2012/001688 which is fully incorporated herein by reference.

Alternatively or additionally, use of a hydrolysis substrate 112including sucrose produces a sugar composition including at least 10%,at least 15% or at least 20% fructose (or intermediate or higherpercentages); and at least 10%, at least 15% or at least 20% sugarsderived from hemicellulose (or intermediate or higher percentages).According to various exemplary embodiments of the invention the sugarsderived from hemicellulose include xylose and/or mannose and/orarabinose. In some exemplary embodiments of the invention, compositionsof this type are provided as an aqueous solution including at least 60%,65%, 70% or 75% dissolved solids. Alternatively or additionally, in someembodiments compositions of this type are provided as an aqueoussolution with at least 40%, at least 50%, at least 60%, at least 70%dissolved solids (or intermediate or higher percentages).

Alternatively or additionally, crude hydrolyzate 130 and/or refinedhydrolyzate 230 are enzymatically treated to convert at least a portionof the glucose therein to fructose. For example, a xylose isomerase(Enzyme commission number EC 5.3.1.5; also known as glucose isomerase)can be used to convert glucose to fructose as is done in the highfructose corn syrup industry.

Some exemplary embodiments of the invention, relate to a sugarcomposition comprising (relative to dry solids) at least 49% glucose; atleast 9.5% xylose; at least 2.5% arabinose; and at least 25% mannose.

Exemplary Viscosity Assay Protocol

In some embodiments of the invention, a comparison is made between asample (e.g. refined hydrolyzate 230) and a reference solution. In orderto make this comparison, a measurement of percentage of total dissolvedsolids in the sample (e.g. hydrolyzate 230) is made (e.g. by evaporationto dryness). If the reference solution is not labeled as to totaldissolved solids concentration, a measurement of the dissolved solidsconcentration in the reference solution is conducted using the samemeasurement technique as for the sample. Once the total dissolved solidsconcentration of the sample and the reference solution are known, thereference solution is adjusted to the same dissolved solidsconcentration as the sample by dilution, or evaporation, as needed. Insome exemplary embodiments of the invention, a 42 Dextrose Equivalents(DE) solution serves as a reference solution. One example of a suitablereference solution is IsoClear® 42% high fructose 80% solids corn syrup(Cargill; Regional Sweeteners Office; Lancaster Pa.; USA).

In some embodiments, a reference solution with a concentration ofdissolved solids higher than the composition being assayed is selected.Use of a reference solution with a higher concentration of dissolvedsolids allows adjustment of the reference solution by dilution.

Once the reference solution and the composition being assayed are at thesame dissolved solids concentration, the viscosity of each is measuredat a given temperature (e.g. 25; 30; 35; 40; 45; 50; 55 or 60° C.). Asugar composition (e.g. refined hydrolyzate 230) with a viscosity atleast 10% lower than a 42 DE reference solution with the same dissolvedsolids concentration (measured under the same conditions) is anexemplary embodiment of the invention.

Exemplary Parameter Assay Considerations

Referring again to FIG. 1, in some embodiments refined hydrolyzate 230is assayed with respect to one or more specific parameters. According tovarious exemplary embodiments of the invention the specific parametersinclude viscosity and/or ash content and/or degradation product leveland/or levels of one or more hemicellulose sugars.

With regard to viscosity, an increase in viscosity can contribute toproblems (e.g. decreased reaction rate and/or decreased yield) inchemically catalyzed conversion processes 233, particularly usingheterogeneous catalyst, where reaction rate AO reaction kinetics arediffusion controlled. Traditionally, implementation of a temperatureincrease during the chemically catalyzed conversion was undertaken in anattempt to mitigate these problems as viscosity typically decreases withtemperature elevation. However, increase of temperature beyond a certainpoint can contribute to undesired degradation of sugars. Elevatedtemperature reactions are more difficult to control and therefore leadto side degradation reactions resulting in undesired products, e.g.large condensation products and coking. Some exemplary embodiments ofthe invention are compositions with at least 40% dissolved solids in anaqueous solution having a viscosity at least 10% lower than a 42 DE(Dextrose Equivalents) reference solution with a same dissolved solidsconcentration at a given temperature.

In some embodiments, a viscosity assay of refined hydrolyzate 230 isused to identify a sugar composition including at least 40%, at least50%, at least 60% or at least 70% dissolved solids having a viscosity atleast 10% lower than a 42 DE (Dextrose Equivalents) solution of similarconcentration at a given temperature. In some embodiments, the dissolvedsolids include at least 20%, at least 30%, at least 40% or at least 50%hemicellulose sugars (or intermediate or higher percentages). In someembodiments, refined hydrolyzate 230 includes at least 10%, 15%, 20%,25% or 30% or more mannose as a percentage of the dissolved solids.Alternatively or additionally, in some embodiments refined hydrolyzate230 includes at least 5%, 7.5%, 10%, 12.5%, or 15% or more xylose as apercentage of the dissolved solids. In some embodiments, a refinedhydrolyzate 230 with a viscosity at or below a pre-determined thresholdlevel is selected for routing to a chemical conversion process 233.Alternatively or additionally, in some embodiments a refined hydrolyzate230 with a viscosity above a pre-determined threshold level is mixedwith a second sugar stream to decrease viscosity and produce a mixedstream suitable for routing to a chemical conversion process 233. Insome embodiments, the second sugar stream includes more non-glucosesugars than refined hydrolyzate 230.

In some embodiments, an assay of organic compounds (e.g. by HPLC or gaschromatography) in refined hydrolyzate 230 is used to identify a sugarcomposition including at least 5, at least 10 or at least 15% organiccompounds (e.g. alcohols, ketones, aldehydes and organic acids including2-5 carbon atoms). While these organic compounds may have an inhibitoryeffect on biological processes, they can be introduced into a chemicalconversion process 233 with little or no effect (Z. R. Ismagilov et al.(2008) Energy Environ. Sci. 1:526-541 and A. Holmen (2009) CatalysisToday 142:2-8). In some embodiments, the organic compounds serve as asubstrate for the chemical conversion process 233 and are converted toadditional conversion product(s). Thus, in some embodiments a refinedhydrolyzate 230 with an organic compounds content at or above apre-determined threshold level is selected for routing to a chemicalconversion process 233. In some embodiments, assay of organic compoundlevels is conducted in conjunction with assay of viscosity.

In some embodiments, an assay of ash (e.g. by complete combustion) inrefined hydrolyzate 230 is used to identify a sugar compositionincluding less than 0.25, less than 0.20, less than 0.15, less than0.10, less than 0.05, less than 0.01 or less than 0.005% ash. Incontrast to organic compounds, increasing the level of ash would not beexpected to have a significant negative impact on biological conversion235, but is expected to contribute to increased catalyst fouling and/orcatalyst poisoning in a chemical conversion process 233. In someexemplary embodiments of the invention, assays of specific ashcomponents are conducted. For example, in some embodiments the assayidentifies refined hydrolyzates 230 including less than 50, less than30, less than 10, less than 5 or less than 1 PPM sulfur. Alternativelyor additionally, in some embodiments the assay identifies refinedhydrolyzates 230 including less than 10, less than 5, less than 3, lessthan 1 or less than 0.1 PPM phosphorus. According to various exemplaryembodiments of the invention assays of ash, or specific components ofash (e.g. sulfur and/or phosphorus), are conducted in conjunction withassays of viscosity and/or with assays of organic compound levels.Multiple assays can be conducted in conjunction with one another bytaking multiple samples and sending each sample to a specific assay inparallel.

In some embodiments, an assay of degradation products (e.g. furfurals)in refined hydrolyzate 230 is used to identify a sugar compositionhaving a relatively high level of degradation products. Assays formeasurement of furfurals include, but are not limited to, gaschromatography and colorimetric assays.

Furfurals have a negative impact on many biological conversion processesbut can serve as a substrate for many chemical conversion processes. Insome embodiments the assay of degradation products identifies refinedhydrolyzates 230 with at least 2%, at least 3%, at least 4% or at least5% total furfurals and/or sugar compositions with not more than 15%, notmore than 12% or not more than 10% total furfurals.

In some exemplary embodiments of the invention, pentoses and/or hexosesare measured in parallel to furfurals so that molar ratio scan becalculated.

In some embodiments, the assay identifies refined hydrolyzates with amolar ratio of furfural to pentoses of at least 0.03, at least 0.05, atleast 0.07 or at least 0.09 and/or refined hydrolyzates 230 with a molarratio of furfural to pentoses less than 0.12 or less than 0.1.Alternatively or additionally, in some embodiments the assay identifiesrefined hydrolyzates 230 with a molar ratio of hydroxymethylfurfural tohexoses of at least 0.03, at least 0.05, at least 0.07 or at least 0.09and/or a molar ratio of hydroxymethylfurfural to hexoses less than 0.12or less than 0.1. In some embodiments, the assay of degradation productsis conducted in parallel with an assay of carboxylic acids andidentifies refined hydrolyzates 230 with a molar ratio of carboxylicacids to sugars of at least 0.03, at least 0.05, at least 0.07 or atleast 0.09 and/or with a molar ratio of carboxylic acids to sugars lessthan 0.12 or less than 0.1. According to various exemplary embodimentsof the invention assays of degradation product level are conducted inparallel with assays of ash (or specific components of ash) and/or withassays of viscosity and/or with assays of organic compound levels.

In some embodiments, an assay of hemicellulose sugars in refinedhydrolyzate 230 is used to identify a sugar composition having arelatively high level of hemicellulose sugars. These hemicellulosesugars originate from module 108 and/or from reactor 110. Hemicellulosesugars are not well utilized by many biological conversion processes 235but can serve as a substrate for many chemical conversion processes 233,e.g. xylose hydrogenation to xylitol or hemicellulose sugars dehydrationto furfural and furfural conversion to levulinic acid.

In some embodiments the assay of hemicellulose sugars identifies refinedhydrolyzates 230 with at least 30, at least 40, at least 50, at least 60or at least 70% hemicellulose sugars relative to total sugars; and 20 to60% cellulose sugars relative to total sugars. According to variousexemplary embodiments of the invention the assay identifies refinedhydrolyzates 230 including at least 10%, at least 15%, at least 20%, atleast 25% or at least 30% mannose relative to total sugars.Alternatively or additionally, according to various exemplaryembodiments of the invention the assay identifies refined hydrolyzates230 including at least 5%, at least 7.5%, at least 10%, at least 12.5%or at least 15% xylose relative to total sugars. Alternatively oradditionally, according to various exemplary embodiments of theinvention the assay identifies refined hydrolyzates 230 including atleast 5%, at least 7.5%, at least 10%, at least 12.5%, or at least 15%fructose relative to total sugars.

According to various exemplary embodiments of the invention assays ofhemicellulose sugar levels are conducted in parallel with assays ofdegradation product level and/or with assays of ash (or specificcomponents of ash) and/or with assays of viscosity and/or with assays oforganic compound levels.

Exemplary Fructose Enrichment

In some embodiments refined hydrolyzate 230 is subjected to fructoseenrichment (e.g. via enzymatic treatment) to produce a compositionincluding at least 10%, 15% or 20% fructose and at least 10%, 15% or 20%hemicellulose sugars.

According to various exemplary embodiments of the invention theresultant composition includes at least 60% dissolved solids and/or atleast 5%, at least 10% or at least 15% of organic compounds as describedabove. In some embodiments, fructose enrichment contributes to areduction in viscosity. Alternatively or additionally, in someembodiments some chemical conversion processes 233 operate moreefficiently with fructose than with glucose.

Exemplary Furfural Concentration Adjustment

As described above, furfurals (or their degradation products such aslevulinic acid) can adversely affect biological conversion 235 but areacceptable in chemical conversion 233 (FIG. 1). In some embodiments,refined hydrolyzate 230 is divided into two portions, one of which isdirected to chemical conversion 233 and another of is directed tobiological conversion 235.

The portion of refined hydrolyzate 230 destined for biologicalconversion 235 is purified to remove furfurals. According to variousexemplary embodiments of the invention, purification to remove furfuralsincludes distillation and/or chromatographic separation. Thispurification reduces the furfural concentration sufficiently that thepurified portion of refined hydrolyzate 230 can be used in biologicalconversion 235.

According to these embodiments, the furfurals removed duringpurification are then added back to the portion of refined hydrolyzate230 destined for chemical conversion 233. In these embodiments of theinvention, a loss of sugar yield from substrate 112 as a result ofdegradation to furfurals during hydrolysis 110 is at least partiallyoffset by conversion of the furfurals to useful products in chemicalconversion 233.

Exemplary Further Processing

FIG. 2 is a simplified flow diagram depicting exemplary methods forfurther processing conversion products indicated generally as 300.

In some exemplary embodiments of the invention, method 300 includesproviding 310 a conversion product (e.g. from a chemical conversionprocess 233 or a biological conversion process 235) and processing 320the conversion product to produce a processed product 330.

In some exemplary embodiments of the invention, the processed productincludes one or more members selected from the group consisting ofterephthalic acid, polymers of terephthalic acid, a fuel ingredient, aparaffin a polyethylene, a polystyrene, a polypropylene, butyl acrylate,butyl acetate, dibutyl phthalate, dibutyl sebacate, other butyl esters,ethylene glycol, monobutyl ether, di-ethylene glycol triethylene glycol,monobutyl ether, isobutyl acetate and butanone (MEK).

In some exemplary embodiments of the invention, the conversion productincludes paraxylene (p-xylene) and processed product 330 includesterephthalic acid. For example, paraxylene can be formed bydehydroaromatization (see for example Z. R. Ismagilov et al. (2008)Energy Environ. Sci. 1:526-541 and A. Holmen (2009) Catalysis Today142:2-8).

A processed product produced by a method as described above is anadditional exemplary embodiment of the invention.

Alternatively or additionally, the depicted further processing method300 can include providing a processed product 330 and subjecting saidprocessed product to an industrial process 340 to produce a downstreamproduct 350 in some embodiments.

In some embodiments, downstream product 350 is a liquid fuel and/or apolymeric plastic.

A downstream product 350 produced by a method as described above is anadditional exemplary embodiment of the invention.

Alternatively or additionally, the depicted further processing method300 includes providing a processed product 330 and using 345 processedproduct 330 as an ingredient or component in a downstream product 350 insome embodiments.

According to various exemplary embodiments of the invention downstreamproduct 350 is a liquid fuel and/or a super absorbent gel and/or a paintand/or a dye, and/or a glue and/or a fabric and/or a plastic item. Forexample, plastic items according to some exemplary embodiments of theinvention may be PET and/or PETA products such as bottles or foodwrappers. Alternatively or additionally, fabrics may be woven ornon-woven fabrics (e.g. as commonly used in moist towelettes).

Downstream product 350 produced by a method 300 as described above areexemplary embodiments of the invention.

It is expected that during the life of this patent many non-enzymaticcatalysts will be developed and the scope of the invention is intendedto include all such new technologies a priori.

Although the invention has been described in conjunction with specificembodiments, many alternatives, modifications and variations will beapparent to those skilled in the art. Accordingly, the applicationembraces all such alternatives, modifications and variations that fallwithin the scope of the appended claims.

Specifically, numerical indicators used in the application could varyeven further based upon engineering principles and/or materials and/orintended use and/or designs incorporated into various embodiments of theinvention. Additionally, components and/or actions ascribed to exemplaryembodiments of the invention and depicted as a single unit may bedivided into subunits. Conversely, components and/or actions ascribed toexemplary embodiments of the invention and depicted assub-units/individual actions may be combined into a single unit/actionwith the described/depicted function.

Alternatively, or additionally, features used to describe a method canbe used to characterize an apparatus and features used to describe anapparatus can be used to characterize a method.

It should be further understood that the individual features describedhereinabove can be combined in all possible combinations andsub-combinations to produce additional embodiments of the invention. Theexamples given above are purely illustrative and do not limit the scopeof the invention which is defined solely by the following claims.Specifically, the invention has been described in some instances in thecontext of sugar mixtures resulting from hydrolysis of cellulosealthough similar mixtures produced by other methods are embodiments ofthe invention.

All publications, patents and patent applications mentioned in thisspecification are herein incorporated in their entirety by referenceinto the specification, to the same extent as if each individualpublication, patent or patent application was specifically andindividually indicated to be incorporated herein by reference. Inaddition, citation or identification of any reference in thisapplication shall not be construed as an admission that such referenceis available as prior art to the present invention.

The terms “include”, and “have” and their conjugates as used herein mean“including but not necessarily limited to”.

EXAMPLES

Reference is now made to the following examples, which together with theabove descriptions; illustrate the invention in a non limiting fashion.

Example 1 Chemical Analysis of Exemplary Compositions

Table 1 provides a summary of chemical analyses of six samples of sugarcompositions according to exemplary embodiments of the invention. Thesecompositions, when used in chemically catalyzed conversion processes cangive results superior to those obtained in similar processes usingpreviously available 42 DE sugar compositions.

TABLE 1 chemical analyses exemplary sugar compositions SAMPLES2011080801 S2011081001 S2011081301 S2011081601 PARAMETER RESULT**S11060601 S11060602 APPEARANCE Clear Clear Colorless Clear ColorlessColorless colorless colorless liquid colorless viscous viscous liquid***liquid liquid*** liquid liquid DS**  76%  78%  77%  80%   69%   73%Monomeric 94.3%  94.1%  93.5%  93.6%  89.7% 87.3 sugars (total) XYLOSE10.5%  10.7%  11.1%  9.9% 13.0% 12.5% ARABINOSE 3.0% 3.0% 3.2% 2.7%4.26% 4.20% MANNOSE 25.4%  26.1%  25.3%  25.0%  26.4% 25.8% GLUCOSE50.5%  49.6%  49.2%  50.9%  38.2% 37.3% GALACTOSE 4.7% 4.7% 4.8% 4.5%7.80% 7.54% FRUCTOSE Not detected Not detected Not detected Not detectedNot Not detected detected GENTIOBIOSE Not detected Not detected Notdetected Not detected Not Not detected detected CELLOBIOSE 0.6% 0.4%0.4% 0.3% Not Not detected detected ISOMALTOSE 0.2% 0.2% 0.3% 0.3% 0.26%0.09% MALTOSE Not detected Not detected Not detected Not detected NotNot detected detected TREHALOSE 1.0% 1.0% 0.06%  1.0% 1.25% 1.35%dimeric 3.9% 4.9% 4.9% 4.9% 5.08% 5.40% sugars(other) trimeric or Notdetected Not detected Not detected Not detected Not Not longer sugarsdetected detected FURFURAL Not detected Not detected Not detected Notdetected Not Not DERIVATIVES detected detected (<0.001%) (<0.001%)ACETIC ACID Not detected Not detected Not detected Not detected 0.033%0.047% ASH 0.094%  0.088%  0.117%  0.097%  **All saccharides resultsrefer to the dry solids (DS). ***At ambient temperature the product mayappear as white opaque liquid, but becomes clearer upon warming.

Example 2 Chemical Analysis of Ash Fraction of Exemplary Compositions

Table 2 provides a summary of chemical analyses of the ash fraction fromthe first four samples presented in Table 1.

TABLE 2 chemical analyses of ash fraction of exemplary sugarcompositions SAMPLE S2011080801 S2011081001 S2011081301 S2011081601 IonRESULT (PPM of total solids) Ca <1 <1 <1 <1 Cu <1 <1 <1 <1 Fe <1 <1 <1<1 K 10 10 11 11 Mg <1 <1 <1 <1 Mn <1 <1 <1 <1 Na 42 38 34 43 P <1 <1 <1<1 S 7 6 7 7 Si 154 152 146 163

Results presented in Table 2 indicate that sulfur and phosphorus levelsin the analyzed samples are exceptionally low.

These results suggest that the exemplary sugar compositions analyzedwill exhibit a low tendency to foul and/or poison catalysts employed inthe relevant conversion processes.

1-29. (canceled)
 30. A composition comprising: (a) at least onewater-soluble monomeric hydrolyzate selected from: (i) a monomerichemicellulose sugar hydrolyzate; or (ii) a monomeric cellulose sugarhydrolyzate; (b) at least one water-soluble dimeric or higher oligomerichydrolyzate selected from: (iii) a dimeric or higher oligomerichemicellulose sugar hydrolyzate; or (iv) a dimeric or higher oligomericcellulose sugar hydrolyzate; and (c) less than 0.25% in total by weight,relative to the total solids in the composition, of ash.
 31. Thecomposition of claim 30, wherein the ash comprises Ca, Cu, Fe, K, Mg,Mn, Na, P, S, and Si.
 32. The composition of claim 30, wherein: thewater-soluble monomeric hydrolyzate is selected from glucose, mannose,or a combination thereof; and the water-soluble dimeric or higheroligomeric hydrolyzate is selected from a dimer or higher oligomer ofglucose, mannose, or a combination thereof.
 33. The composition of claim30, wherein: the water-soluble monomeric hydrolyzate is selected fromglucose, mannose, galactose, or a combination thereof; and thewater-soluble dimeric or higher oligomeric hydrolyzate is selected fromcellobiose, isomaltose, trehalose, or a combination thereof.
 34. Thecomposition of claim 30, wherein: the water-soluble monomerichydrolyzate is selected from glucose, mannose, galactose, fructose, or acombination thereof; and the water-soluble dimeric or higher oligomerichydrolyzate is selected from cellobiose, isomaltose, trehalose, or acombination thereof.
 35. The composition of claim 30, wherein thewater-soluble monomeric hydrolyzate is derived from a lignocellulosesubstrate.
 36. The composition of claim 30, further comprising water.37. The composition of claim 30, wherein the water-soluble monomerichydrolyzate is present at a concentration of at least 90% in an aqueoussolution.
 38. The composition of claim 30, wherein the water-solublemonomeric hydrolyzate is glucose, galactose, mannose, fructose, or amixture thereof.
 39. The composition of claim 30, further comprisingless than 0.10% by weight, relative to the total solids in thecomposition, of ash.
 40. The composition of claim 30, further comprisingless than 1 ppm by weight, based on the total weight of the total solidsin the composition, of calcium.
 41. The composition of claim 30, furthercomprising less than 1 ppm by weight, based on the total weight of thetotal solids in the composition, of iron.
 42. The composition of claim30, further comprising less than 50 ppm by weight, based on the totalweight of the total solids in the composition, of sulfur.
 43. Thecomposition of claim 30, wherein the weight ratio of the water-solublemonomeric hydrolyzate to the ash is greater than about 360:1.
 44. Acomposition comprising: (a) at least one water-soluble monomerichydrolyzate selected from: (i) a monomeric hemicellulose sugarhydrolyzate; or (ii) a monomeric cellulose sugar hydrolyzate; (b) atleast one water-soluble dimeric or higher oligomeric hydrolyzateselected from: (iii) a dimeric or higher oligomeric hemicellulose sugarhydrolyzate; or (iv) a dimeric or higher oligomeric cellulose sugarhydrolyzate; and (c) impurities, wherein the impurities comprise: lessthan 1 ppm by weight, based on the total weight of the total solids inthe composition, of calcium; less than 1 ppm by weight, based on thetotal weight of the total solids in the composition, of iron; less than50 ppm by weight, based on the total weight of the total solids in thecomposition, of sulfur; and less than 0.25% by weight, based on thetotal weight of the total solids in the composition, of ash.
 45. Thecomposition of claim 44, wherein the impurities comprise Ca, Cu, Fe, K,Mg, Mn, Na, P, S, and Si.
 46. The composition of claim 44, wherein: thewater-soluble monomeric hydrolyzate is selected from glucose, mannose,or a combination thereof; and the water-soluble dimeric or higheroligomeric hydrolyzate is selected from a dimer or higher oligomer ofglucose, mannose, or a combination thereof.
 47. The composition of claim44, wherein: the water-soluble monomeric hydrolyzate is selected fromglucose, mannose, galactose, or a combination thereof; and thewater-soluble dimeric or higher oligomeric hydrolyzate is selected fromcellobiose, isomaltose, trehalose, or a combination thereof.
 48. Thecomposition of claim 44, wherein: the water-soluble monomerichydrolyzate is selected from glucose, mannose, galactose, fructose, or acombination thereof; and the water-soluble dimeric or higher oligomerichydrolyzate is selected from cellobiose, isomaltose, trehalose, or acombination thereof.
 49. The composition of claim 44, further comprisingless than 0.10% in the total weight relative to the total solids in thecomposition, of ash, wherein the ash comprises Ca, Cu, Fe, K, Mg, Mn,Na, P, S, and Si.
 50. The composition of claim 30, comprising at leastone dimeric hydrolyzate.
 51. The composition of claim 30, wherein one ormore of the hydrolyzates is a hexose.
 52. The composition of claim 30,wherein one or more of the hydrolyzates is a pentose.
 53. Thecomposition of claim 30, wherein: the water-soluble monomerichydrolyzate is selected from xylose, arabinose, or a combinationthereof; and the water-soluble dimeric or higher oligomeric hydrolyzateis selected from a dimer or higher oligomer of xylose, arabinose, or acombination thereof.
 54. The composition of claim 39, wherein: thewater-soluble monomeric hydrolyzate is selected from xylose, arabinose,or a combination thereof; and the water-soluble dimeric or higheroligomeric hydrolyzate is selected from a dimer or higher oligomer ofxylose, arabinose, or a combination thereof.
 55. The composition ofclaim 40, wherein: the water-soluble monomeric hydrolyzate is selectedfrom xylose, arabinose, or a combination thereof; and the water-solubledimeric or higher oligomeric hydrolyzate is selected from a dimer orhigher oligomer of xylose, arabinose, or a combination thereof.
 56. Thecomposition of claim 41, wherein: the water-soluble monomerichydrolyzate is selected from xylose, arabinose, or a combinationthereof; and the water-soluble dimeric or higher oligomeric hydrolyzateis selected from a dimer or higher oligomer of xylose, arabinose, or acombination thereof.
 57. The composition of claim 42, wherein: thewater-soluble monomeric hydrolyzate is selected from xylose, arabinose,or a combination thereof; and the water-soluble dimeric or higheroligomeric hydrolyzate is selected from a dimer or higher oligomer ofxylose, arabinose, or a combination thereof.
 58. A compositioncomprising: at least one water-soluble monosaccharide hydrolyzate; atleast one water-soluble disaccharide hydrolyzate; and less than 0.25% intotal by weight, relative to the total solids in the composition, ofash.
 59. The composition of claim 58, wherein the ash comprises Ca, Cu,Fe, K, Mg, Mn, Na, P, S, and Si.